Novel m-(3,3-disubstitutedureido)phenyl(alpha-cyanoalkyl)carbamates and method for the control of undesirable plant species therewith

ABSTRACT

THE PRESENT INVENTION RELATES TO NOVEL M-(3,3-DISUBSTITUTEDUREIDO)PHENYL (A-CYANOALKYL)CARBAMATES AND TO A METHOD FOR THE CONTROL OF UNDESIRABLE PLANT SPECIES THEREWITH. THE INVENTION FURTHER RELATES TO A METHOD FOR THE PREPARATION OF THE ABOVE-SAID COMPOUNDS.

United States Patent 3,823,178 NOVEL m-(3,3 DISUBSTITUTEDUREIDO)PHENYL (a-CYANOALKYL)CARBAMATES AND METHOD FOR THE CONTROL OF UNDESIRABLE PLANT SPECIES THEREWITH Karoly Szabo, Stiegengasse 4/16, A-1060, Vienna, Austria, and Venkat Rao Gauti, 21 Caton Drive, Dewitt, N.Y. 13214 No Drawing. Filed May 8, 1972, Ser. No. 251,489 Int. Cl. C07c 121/52 US. Cl. 260-465 D 7 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to novel m-(3,3-disubstitutedureido)phenyl (u-cyanoalkyDcarbamates and to a method for the control of undesirable plant species therewith.

The invention further relates to a method for the preparation of the above-said compounds.

This invention relates to novel compounds having the formula:

where R is methyl or ethyl, or when taken together with R forms a rycloalkyl C -C R is alkyl C -C cycloalkyl C -C or where R, is hydrogen, halogen, or loweralkyl C -C n is an integer selected from 0, l, and 2 and m is an integer selected from 0, l, 2, and 3; R is an alkyl radical C -C and R represents a member selected from the group consisting of alkyl C -C and alkoxy C -C The invention also relates to a novel method for controlling undesirable plant species with the above-identified compounds and to a novel method for the preparation of said compounds.

In accordance with the invention, the ureido phenyl carbamates having the above structure can be prepared from wcyano esters of isocyanic acid or 'a-cyanoalkylcarbamoyl halides having the structure:

where R, and R are as described above, and R is NCO or NHCOCl. These compounds and the preparation 3,823,178 Patented July 9, 1974 therefor are described in our copending application, Ser. No. 251,480 filed simultaneously with the present applica-- tion. The active compounds are readily prepared by reacting said a-cyanoalkylcarbamoyl halide, or isocyanic acid ester with a ureido phenol in aprotic solvents (for example, ketones, aromatic hydrocarbons, and ethers), such as acetone, ethyl acetate, benzene, toluene, diethyl ether, tetrahydrofuran, or the like. The reaction is carried out in the presence of a weak base catalyst, such as sodium carbonate, potassium carbonate, or an organic tertiary amine, such as triethylamine. The reaction is usually exothermic and does not require heating. Graphically, it may be illustrated as follows:

where R, R R R and R are as described above.

In practice, we have found that the herbicidally active ureido phenyl carbamates can also be readily prepared by first reacting the appropriate ketone with an alkali metal cyanide, such as sodium or potassium cyanide, and an ammonium salt, preferably the halide or sulfate, in the presence of ammonium hydroxide. The reaction is generally conducted in aqueous solution or in an aqueous-alcoholic mixture, the alcohol preferably being a loweralkanol of from 1 to 4 carbon atoms. Although the reaction may be carried out at room temperature, it is frequently found desirable to heat the reaction mixture to about 40 C. to C., but preferably 40 C. to 55 C. This reaction yields the aminonitrile corresponding to the ketone employed. The reaction is graphically illustrated below using KCN as the alkali metal cyanide and ammonium hydroxide as the base.

where R and R are as described above.

Where desired, the aminonitrile is converted to its hydrohalide salt, preferably its hydrochloride salt, by dissolving the free base in anhydrous ether; for example, diethyl ether, tetrahydrofuran, or ethyl ether, and then admixing with said solution the desired hydrohalide. Generally, it

is most convenient to mix the acid with anhydrous ether and add this mixture to the ether solution of aminonitrile. The hydrohalide salt precipitates and can be filtered E.

The aminonitrile or the hydrohalide salt thereof is then dissolved or dispersed in an aprotic solvent, such as acetone, ethyl acetate, benzene, toluene, diethyl ether, tetrahydrofuran, or the like. This solution is then cooled to about 0 C. to C. and treated with phosgene gas or a solution of phosgene in aprotic solvent, or both.

The reaction is conducted at a low temperature, preferably about 0 C. to 10 C., although lower temperatures may be used. When admixture of the phosgene with the aminonitrile has ben completed, the carbamoyl chloride corresponding to the aminonitrile is present in solution and can be recovered therefrom if desired or converted to the isocyanate by heating the reaction mixture to refluxing temperature. Generally, about 1 to 2 moles of phosgene per mole of aminonitrile is satisfactory for the reaction, which is graphically illustrated as follows:

where R and R are as described above.

In the preferred process, however, the ureido phenol having the formula:

where R and R are as described above, is dissolved or dispersed in an anhydrous aprotic solvent, such as acetone, methylbutyl ketone, ethyl acetate, benzene, toluene, diethyl ether, tetrahydrofuran, or the like, and the mixture added to the cold solution of carbamoyl chloride. The thus-formed reaction mixture is then treated with weak base, preferably sodium or potassium carbonate. As this latter reaction is generally exothermic, heating of the reaction mixture is not usually required. The ureido phenyl carbamate formed in this reaction can then be recovered from the reaction mixture by any convenient means, such as by filtration, centrifugation, or the like.

The m-(3,3-disubstituted ureido)phenyl (u-cyanoalkyD- carbamates of the present invention are highly effective herbicides. They may be used as preemergence herbicides by applying a herbicidally effective amount thereof to soil containing seeds of undesirable plants. They are also effective postemergence herbicides when applied in herbicidally elfective amounts to the foliage and plant parts of plants sought to be controlled.

The compounds may be formulated as dusts, generally containing from about 1% to by weight of the active compound and from about 99% to about 85% by weight of a diluent, such as attaclay, bentonite, talc, kaolin, diatomaceous earth, or the like.

They may also be prepared as wettable powders 'by grinding about to 75% by weight of the active material with about 23% to about 73% by weight of a diluent, such as mentioned above, and admixing therewith about 1% to about 5% by weight of an anionic-nonionic emulsifier or surfactant and about 1% to 5% by weight of a dispersing agent, such as an alkali metal lignosulfonate. The wettable powder is generally dispersed in water and applied as a liquid spray in sufficient amount to provide from about 0.5 to 20 pounds per acre of active material, and preferably 0.5 to 8 pounds per acre of said material.

The active compounds can also be made up as discrete granular particles on carriers, such as sand, ground corn cobs, diatomaceous earth, attaclay, or the like. Such formulations are particularly useful as preemergence herbicide formulations when applied in amounts suflicient to provide from about 0.5 to 20 pounds per acre, and preferably 0.5 to 8 pounds per acre of active material.

The following examples are given primarily by Way of illustration. No specific details or enumeration contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated.

EXAMPLE 1 2-Amino-2,3,3-trimethylbutyronitrile onmot lom KCN NH4C1 NI-LOH To a two-liter flask is added 66 grams of KCN dissolved in 120 ml. of water, along with a magnetic stirring rod. When almost all of the cyanide is dissolved, 140 ml. of water containing 61 grams of NH Cl is introduced into the flask followed by the addition thereto of 67 ml. of concentrated ammonium hydroxide. A solution of the ketone, i.e., 100 grams of pinacolone in 150 ml. of methanol, is added to the mixture and stirred. The mixture was heated to 45 C. to 55 C. for 18 hours and the 1 solvent evaporated to yield the product, a dark heavy oil.

The hydrochloride salt is then obtained by dissolving the oil in anhydrous diethyl ether and admixing therewith hydrochloric acid, preferably in anhydrous diethyl ether. The mixture is filtered and the solvent removed by evaporation under reduced pressure leaving the hydrochloride salt of the aminonitrile.

EXAMPLE 2 2-Amino-2-methylbutyronitrile Methyl ethyl ketone (72 grams) is mixed with 73 grams of ammonium sulfate. To this suspension is then added 200 ml. of solvent ether. The mixture is then stirred at 20 C. to 25 C. (slight cooling). A solution of sodium cyanide (50 grams in 200 ml. of water) is then added dropwise during one hour and the reaction mixture stirred for 7 to 10 hours. The inorganic salts are filtered off and the aqueous layer extracted three times with 200 ml. portions of ether. All other extracts are combined, dried over anhydrous potassium carbonate, and then concentrated by evaporation under vacuum.

The residue is distilled at 15 mm. to give 45 to 50 grams of product with boiling point 68 C.

EXAMPLE 3 Following the procedure of Example 1, but substituting the appropriate ketone for pinacolone, yields the corresponding aminonitriles reported in Table I below. The hydrochloride salts of each are likewise prepared as described in Example 1.

TABLE I Ketone/Amm' onitrile R R Methyl Methyl Methyl Isopropyl Methyl Phenyl Ethyl Butyl Cyclohexyl Cyclopentyl Methyl t-Butyl Methyl n-Propyl Methyl Sec.-buty1 Methyl Benzyl Methyl Phenethyl Ethyl Benzyl Methyl Cyclopropyl Methyl 2 ethylbutyl Ethyl Cyclobutyl Methyl p-Chlorophenyl Methyl 2,3-dichlorophenyl Methyl p-Chlorophenethyl Ethyl 2-ethylhexyl Methyl 3-methylbutyl EXAMPLE 4 1-Cyano-1,2-dimethylpropyl isocyanate E E CH;-C-CH(CH'): 0001, cnr-c-cmclion NHI'HCI NHCOCI CN om-o-omonm NCO Forty-one grams of 2-amino-2,3-dimethylbutyronitrile hydrochloride is dispersed in 220 ml. of ethyl acetate. The

1-Cyano-1,2,2-trimethylpropyl isocyanate Following the procedure of Example 4 and substituting 2-amino-2,S-dimethylbutyronitrile for 2 amino-2,3-dimethylbutyronitrile yields l-cyano-1,2,2-trimethylpropyl isocyanate. Boiling point 77 C. to 80 C. at 1 to 2 mm.

6 EXAMPLE .6

1-Cyano-1,3-dimethy1butyl isocyanate NH: 1 0001: CH; -CHz-CHCH NCO A NHCOCI CHg-(J-CHr-CH-CH; cm-o-om-(JH-cm CN CH; CN H:

25.2 Grams of 2-amino-2,4-dimethylpentanonitrile is dissolved in 100 ml. of anhydrous ether; 50 ml. of ether saturated with HCl is then added. The precipitated HCl salt is filtered off and dried in a desiccator. The total HCI salt is then used for the conversion to isocyanate using anhydrous reagent grade ethyl acetate as solvent.

The HCl salt is dispersed in 100 ml. of the ethyl acetate and slowly added to a stirred, cold (0 C. to 5 C.) solution of phosgene grams) in 150 ml. of ethyl acetate. Stirring is continued for one hour, then cooling discontinued and the reaction mixture refluxed.

The mixture is cooled and the solvent evaporated under reduced presure. The residue is extracted with hot hexane and the product recovered by distillation. The product has a boiling point of 47 C. to 54 C./0.75 mm.; n 1.4460.

EXAMPLE 7 I-Cyano-l-methylpropyl isocyanate Z-Amino 2 methylbutyronitrile (39.2 grams) is dissolved in ml. of dry ethyl acetate and added dropwise to a solution of 80 grams of phosgene in ml. of ethyl acetate with vigorous stirring during one hour. The temperature should not be allowed to go over 5 C.

After all the aminonitrile is added, the cooling is discontinued, phosgene gas passed in, and the mixture heated to reflux. Almost all the solid goes into solution, resulting in a golden yellow color. The time of passage of phosgene is 2 to 2 /2 hours.

Most of the ethyl acetate is removed by distillation by heating on a water bath, leaving a thick viscous residue, which on distillation yields the product, boiling point 54 C. to 56 C. at 12 to 14 mm.; 11 1.4165.

This procedure is followed with appropriate aminonitrile substitution to yield the esters of isocyanic acid and isocyanates, reported in Table H.

TABLE II C0012, 0 C. to a-Cyanoalkylcarbamoyl Isocyanate Amlnonltrlle ethyl acetate halide Reflux Isocyanate characterization CN 0001:, 0 0. CN Reflux..-. 0N B.P. 8688 C. at

l to 5 0., I 1.25 mm. C-CH: ethylaeetate. -CCH: C-CH;

NHz-HCR NHCOCl NC 0 CH: .....-d0.....::";: (i/Ha ..'.-.d0-...- CH: B.P. 144-145 C.

CN ON ON ON .'.:'..d0.....::: CN ..'...d0..... ON .1. 62 C. at

0.7-1 mm. NHa-HCI NHCOCI NCO CN .:::.fi0....-:::: CN .:...d0 CN 3.1. 52-54 C. at;

NHrHCl NHCOCI NC 0 N .:.-..do CN -d0..... (3N B.1P.26980 G. at

mm. CHz-CHa-C-CHz-OHa-CHrCH: CHzCH2 1)8C HrC 2( 2)a a NHz'HCl NHCOCl NCO 7 EXAMPLE 8 m- (3,3-Dimethylureido) phenyl I-Cyanol-methylpropyl carb amate B: N-o-N-(cm OCN- "oH,-cn, new. it n.

o H CH: o-ii-iz- -oN l-CH:

To a suspension of 1,1-dimethyl 3-(m-hydroxyphenyl)- urea (620 mg.) in ml. of dry reagent grade acetone, a

drop of triethylamine is added, followed by 420 mg. of l-cyano-l-methylpropylisocyanate all at once. The reaction is very exothermic and a clear solution results. After standing for minutes, a crystalline mass comes out of solution. The product (1.0 gram) is filtered off and washed with ice-cold acetone to give a melting point of 145 C. to 147 C.

EXAMPLE 9 m- (3-Methoxy-3-methylureido phenyl l-cyanol-methylpropyl)-carbamate O H CN O-ii-llT--CHwCH:

OIL catalyst 1.96 Grams of 3-(m-hydroxyphenyl) 1 methoxy-lmethylurea is dissolved in ml. of acetone, a few drops of triethylamine are added, followed by 1.25 grams of the l-cyano-1-methylpropylisocyanate. The reaction is exothermic. The reaction mixture is refluxed for one hour and then cooled. The mixture on cooling deposits a crystalline product, which is filtered off, and washed with icecold acetone to give 2.4 grams with melting point 147 C. to 149 C.

The mother liquors on dilution with an equal volume of hexane, yield more of the product melting at the same temperature.

To 10 ml. of anhydrous acetone is added, first, 1.95 grams of the 3-(m-hydroxyphenyD-l-rnethoxy-l-methylurea and then 1.3 grams of l-cyano-l-methylethylisocyanate. Three drops of t-riethylamine is then added to the mixture and a mildly exothermic reaction occurs. A white solid product precipitates'which is collected and dried. The yield is 2.5 grams of product, melting point 165 C. to 167 C.

EXAMPLE 1 1 m- 3-Methoxy-3-methylureido phenyl 1-cyano-1- mthylethyDcarbamate 7 CH3 CH JNH1 0001; Nazoo.

CH: J: :l EtlN CHa NHCOO1 I OCH; CN

Q-NHCON CH3 (|)CONH(i3-CEN NHGONCHa(OCH To a phosgene solution (12 grams, 0.12 mole) in dry ethyl acetate (180 ml.) cooled to 0 C. is added anhydrous sodium carbonate (1.5 grams, 0.14 mole) then dropwise with cooling Z-methyl 2 aminopropionitrile (8.4 grams, 0.1 mole) in ethyl acetate (40 ml.). A white solid is formed during the additionl After one hour the reaction mixture is allowed to attain reaction temperature (20 0.). Then it is gradually warmed to 60 C. taking 30 minutes. Further phosgene is passed through the mixture for a further 30 minutes at 60 C. to 67 C. and the reaction mixture becomes clear, is filtered and evaporated under reduced pressure to a colorless oil. The infrared spectrum shows very intense absorption at 1740 to 1780 cm." assignable as the carbamoyl chloride (Ci-Cl g oup) The crude carbamoyl chloride is added to 3-(m-hydroxyphenyl)-1-methoxy-1-methyl urea (17.64 grams, 0.09 mole), triethylamine (11 grams, 0.11 mole) in ethyl acetate (50 ml.) at 25 C. A solid precipitates, further triethylamine (20 grams, 2 moles) is added and the reaction mixture temperature rises to 33 C. The reaction is cooled to 18 C. for 30 minutes and filtered. The solid is stirred with water and dried to give 20.1 grams melting point 167 C. to 168 C. The filtrate is evaporated almost to dryness, then water-acetone added and a further 2.3 grams (9%), melting point 157 C. to 160 C., is obtained. Total yield 22.4 grams (89%).

TABLE III H NCO EtaN 0 H ON Ethyl acetate II I l R1?R1 --r 0-C-N(|1R /R| CN R: NH-fi-N\ /R4 0 R; NH-C-N Characterized Melting R4 R R1 R2 R1 R: R4 R5 point, C.

CH; CH; (R1 and R2 together) (R1 and R1 together) CH: CH: 159-162 CH; CH; CH; Q 0H; Q CH: CH; 164-167 CH. CH; CH; -OH(CH;): CH; -CHCH=)1 CH: CH; 157-159 OH; OCH: CH; -CH(CH:)1 CH: -CH CH3): CH: OCH: 142-144 OH, OCH; 0 (R1 and R1 together) 0 (R1 and R1 together) CH| OCH; 161-163 CH1 OCH] CHl Q CH: Q CH; OCH! 118-121 CH; CH; O (R; and R1 together) 0 (R1 and R3 together) CH; CH: 170-171 CH; CH, (R1 and R1 together) (Br and R1 together) OH: OCH. 161-16 CH, CH: 01H; -CH,CH,CH,CH; 0 H; CHaCH2CH2CHa CH: CH: 164-166 EXAMPLE 12 EXAMPLE 13 The postemergence herbicidal activity of the compounds of the present invention is demonstrated by the following tests. In said tests, ten-day old crabgrass, yellow foxtail, wild oats, mustard, bindweed, and bush bean plants are sprayed with /65% water/acetone solutions of test compound. Each fiat is sprayed with 15 ml. of solution containing 50 mg. of compound. The sprayed plants are then placed on greenhouse benches and cared for in accordance with normal greenhouse procedures. Three weeks after treatment, all plants are examined and rated. The results obtained appear in Table IV below.

TABLE IV.P0 STEMERGENCE ACTIVITY The postemergence herbicidal activity of the compounds of the present invention is demonstrated by the following tests. A variety of monocotyledonous and dicotyledonous plants, approximately two weeks old and growing in flats, are sprayed with 35%/ aqueous acetone mixtures containing test compound in sufiicient concentration to provide the equivalent of 0.5, 1.0, or 4.0 pounds of active compound per acre, when sprayed on the flats for a given period under 86 p.s.i.g. pressure.

After spraying, the flats are placed on greenhouse benches and cared for in accordance with normal green- 2s1ight effect 11-25 5definite injury 41-60 Based on visual determination of stand, size, vigor,

chlorosls, growth malformation, and over-all plant appearance.

Percent Dilference in Growth from the Check 1 ban a 5 on the rating Ratings wo BA FOX MI RAG MU LA Rating Sytem:

0no .efiect 1-possible effect 3--moderate effect 26-40 6herbicidal efiect 61-75 7-good herbicidal elfect 76-90 8approaching complete kill 91-99 9-comp1ete kill 5 Abnormal growth, 1.02., a definite ghysiological malformatlon but with an over-all efiect less scale.

MG COT SB SOY COR house practices. Three weeks after treatment, the plants Plant Species TABLE V.POSTEMERGENCE ACTIVITY LbsJacre rate are examined and rated according to the index given below.

MG Annual morning glory. 5 COT Cotton. SB Sugar beet.

SOY Soybean.

COR Corn.

W0 a Wild oats.

BA ..n.. Barnyardgrass.

FOX Green foxtail.

MI Foxtail millet.

RAG Ragweed.

LA Lambs-quarters.

Compound HCN OCH:

500 ELL CHa TABLE V-Cntinued Ratin Lbs/acre gs Compound rate MG 00'! SB SOY COR wo BA FOX MI RAG MU LA CN 0.5 9 9 9 9 9 s a s 9 9 9 0 H 1.0 9 9 9 9 9 8 9 0 8 9 9 9 II I 4.0 9 9 9 9 3 9 9 9 9 9 9 9 O--CN CH3 NH-fi-N\ 0 H CN 0.5 9 9 9 9 8 s 9 9 9 l 1 1.0 9 9 9 9 9 9 9 s s 9 9 9 0c-N- -CH; a0 9 9 9 9 9 9 9 9 9 9 9 CHz-CH:

NH|CN(CH;)9

0 H CN 0.5 a 9 1 5 9 9 9 J 1.0 9 9 s 9 2 5 a 2 3 9 9 9 CN- 4.0 9 9 0 8 8 7 9 9 9 CH9 NH-fi-N\ 0 H 0N 0.5 1 1 1 0 0 a 1 0 9 1 1.0 2 a 1 1 0 0 1 2 2 s 1 o OCN CH| 4.0 1 2 1 3 0 7 8 0 (EH-( H9):

NH-(fi-N-(CHO:

o H CN 0.5 0 0 0 0 0 0 0 0 1 5 n I; 1.0 1 1 a 1 0 0 0 0 0 0 a 0 OC-N- 4.0 1 3 0 7 2 1 1 7 9 7 0011. NH(I%N\ 0 H ON 0.5 0 0 0 0 0 0 0 0 0 H I I 1.0 n 0 0 0 0 0 0 0 0 0 6 1 ?C-NCCH9CH1CH9-CH| 4.0 O 0 0 0 0 0 0 9 2 CH -CH;

CH: NH(l'IJ-N\ EXAMPLE 14 acetone/water mixture containing 1% of the surfactant The preemergence herbicidal activity of the compounds of the present invention is demonstrated by the following tests. In said tests, seeds or crabgrass, corn, watergrass, wild oats, bush beans, Indian mustard and curled dock are 70 T'wene and mg. of test compound. This treatment provides the equivalent of 20 pounds per acre of test compound. After spraying, the flats are placed on greenhouse benches and cared for in accordance with conventional greenhouse procedures. Three weeks after spraying, the

planted in flats. The seeded flats are then sprayed with an flats are examined and rated for herbicidal activity.

TABLE VI Percent kill Crab- Water- Mus- Wild Curled Bush Compound grass grass tard Corn oats dock beans 0 H CN 100 100 100 100 100 100 100 Chi-9.91.019: CH;

O CH;

NH-CN I CH3 0 H CN 100 100 100 100 100 100 O --I IC ICHa Hg-OH;

NH-CN(OHI)2 1 No test.

EXA'MPIJE '15 65% acetone/water) containing test compound. The concentrations are such as to provide the equivalent of 0.5, The preemergence herbicidal activity of the compounds 25 1,0 01- 4,0 pounds per acre of acre of active compound of the invention is demonstrated in the following tests. h sprayed at 86 p.s.i.g.

Seeds of a variety of monocotyledonous and dicotyledon- After spraying, the pots are placed on greenhouse benchous plants are mixed with potting soil and planted in pl'aS- es and cared for in routine fashion. Four weeks after tic pots on top of about one inch of potting soil. The treatment, the pots are examined and rated according to seeded pots are then sprayed with a test solution (35 30 the index given above.

TABLE VIL-PREEMERGENCE HERBICIDAL ACTIVITY Ratings Lbs/acre Compound rate MG COT SB SOY COR wo BA FOX MI RAG MU LA 0 H CN 0.5 1 1 9 o 5 7 9 s 8 9 9 9 II I I 1.0 7 s 9 9 9 9 9 9 9 9 9 9 (|)CN-(I3CH; 4.0 9 9 9 9 9 9 9 9 9 9 9 OCH: NHC--N II 0 0H,

0 H CN 0.5 1 1 o 7 a II I I 1.0 2 2 9 2 5 s 9 9 7 7 9 8 (|)-0N(|3CH1 4.9 9 9 9 9 9 Oman,

/CH9 NH?|J-N\ 05 o 0 o o o 5 o 0 a 0 H 10 9 9 o a o o 7 0 9 0 9 a II I 40 0 5 5 7 7 6 9 9 0CN CH1 NH-( 3-N H ON 05 o o 0 o o o 0 '0 II I 10 0 1 0 1 0 o 0 o 0 0 9 9 0--c--N- 4.0 a 2 9 o 0 8 9 CH3 NH-( J-N 0 E CN 0.5 o e 0 0 0 o 0 5 9 a I 1.0 2 2 0 2 o a s 1 0 9 9 7 00NCOH9 4.0 9 9 9 9 6 9 9 9 8 TABLE VI-Contlnued Ratings Lbs/acre Compound rate MG co'r SB SOY COR wo BA FOX MI RAG MU LA H 0N 0.5 0 0 s 1 o 7 9 9 s 9 s H I 1.0 9 3 9 9 s 7 9 9 s 9 9 9 )-0NO-0H2CH; I 4.0 9 9 9 5 9 9 9 9 9 9 9 9 OCH: NH-|J-N\ CHI 0 H CN 95 0 9 0 3 a o 0 9 7 5 1.9 9 9 9 9 9 7 s 1 1 s 9 8 (|)-CN I c H-(CHs) 1 1 0 9 9 9 s 9 9 9 9 9 OCH: -NH("3N\ 0 CHI 0 H ON 0.5 o o 0 9 9 o 9 o 1 n 1.9 0 1 0 9 0 1 2 1 1 1 9 7 CN 4.9 9 9 9 9 7 s 9 s 9 OCH: -NHfi-N\ 0 H ON 95 o 0 9 0 9 0 o 0 1 l 1 9 9 0 o o o 9 0 0 0 0 9 2 ('i CN-I- 4 0 1 s 1 1 2 s 9 /OCH9 NH( 3N 0 H N 95 9 0 o 0 0 o 1 1 3 u I 1 o o 0 o o 0 0 9 2 0 2 s 5 O0N 19 9 5 9 3 a 9 1 s 9 s /OCH| NHfi-N 0 H CN 9.5 9 0 o 0 0 0 0 9 9 0 1 5 11 1.0 1 1 3 1 o 9 0 0 9 o 9 6 OCN 1 a 9 7 1 7 9 7 OCH; N H("3-N\ 0 H CN 9.5 0 0 0 9 9 9 o 0 0 0 0 A: 1.9 9 o 9 9 o 9 9 9 9 9 9 1 OCN -CH2CH2-CH2CH: 4.0 0 0 0 0 0 0 0 9 Hz-CH! NHON We claim: wherein R represents a member selected from the group 1. A compound having the formula: consisting of methyl and ethyl, or when taken together with R forms a cycloalkyl C -C R represents a member selected from the group consisting of alkyl C -C OC-NC-R cycloalkyl C -C or R: l)m

where R is halogen, or loweralkyl C -C n is an integer R6 selected from O, -1, and 2; m is an integer selected from 19 0, 1, -2, and 3; R represents an alkyl radical C -C and R represents a member selected from the group consisting of al kyl C -C and alkoxy C -C 2. A compound according to Claim 1, m-(3-methoxy- 3-mcthy1ureido)phenyl (l-cyano \1 methylcthyDcarbamate.

3. A compound according to Claim 1, m-(3,3-dimethylurcido)phenyl l-cyanocyclohexyl)carbamate.

4. A compound according to Claim 1, mP('3, 3-d*i'mcthy1- ureido)p11enyl (l-cyano-l mcthylpropyl)car'bamate.

5. A compound according to Claim 1, m"('3,B-dimcthylureid0)phenyl (a-cyano-a-methylbenzyl)carbamatc.

6. A compound according to Claim 1, m-(3-methoxy- 3-met-hylurcido)phenyl ('l-cyano 1 methylpropyDc'arham-ate.

7. A compound according to Claim 1, m-(B-methoxy- 3-methylurcido)-phenyl (1cyano 1,=2 di'methylpropyl) carbamate.

References Cited UNITED STATES PATENTS 3,317,583 5/(1'967 Hsi 260-465 D 3,488,376 1/ 1970 Ulrich 260-465 "D X 3,625,992 '12/197'1 Duerr ct a1 260-465 D X 3,577,453 5/1971 Rohr et a1. 240-465 D 3,304,225 2/1967 Szabo et a1. 260-465 D X 3,551,477 12/ 1970 Koen'ig et a1. 260-465 DX JOSEPH P. BRUST, Primary Examiner "US. Cl. X.-R. 

